The-rhiite



Patented May 21, 1929.

UNITED STATES PATENT OFFICE.

1.: in ALBERT none, or MANNHEIM, AND KARL KoBnnLn, or LUDWIGSHAFEN-ON- THE-RHINE, GERMANY, nssrenons 'ro GnAssnLLr nsnsrnrr CORPORATION, or new YORK, 1v. Y., A CORPORATION or nnnawnnn PRODUCTION OF VAT DYESTUFFS.

Ho Drawing.

lil eso-benzdianthrono, obtainable by the reduction oi 1.llianthraquinonyl, and also the derivatives of ms-benzdianthrone hitherto known posses an aiiinity for the libreand a tinctorial power which remain far below those required in the case of vat dyestutls. Also the tctrabroine ms benzdianthrone which has been produced by brominating benzdianthrone, using the most rigorous methods of working, gives from a green vat colorations which do not meet the requirements put to dyestuffs in practice.

We have now found that by treating msbenzdianthrone and its derivatives with halogen or substances liberatii halogen, at atmospheric pressure and pre'rerably in the presence of a halogen transporter, halogen derivatives are produced, the tinctorial properties of which meet all requirements of practice. In the manner described more or less highly halogenated derivatives can be obtained.

The most valuable products obtainable according to the present invention are the trihalogen derivatives and those monoor poly halogenated ms benzdianthrones which, in addition to the halogen atoms, con tain one or more other substituents such as allrvl groups, alkoXy groups and others.

We do not claim in this aplication halogenated benzdianthrones tree from other suostituents, said compounds being claimed in a divisional application.

The following examples will further illustrate how our invention may be carried out in practice, but the invention is not limited to these examples. The parts are by weight.

E sample 1.

100 parts of bromine are introduced, drop by drop, into a solution of 100 parts of msbenzdianthrone in 1000 parts of nitrobenzone at room temperature. The mass is stirred for one hour, whereupon the temperature is raised 60 C. and stirring continued this temperature for three further hours. The reaction product is then allowed to cool. The brownish-black crystals, which separate out, consist of the hydrobromic acid oxonium salt of dibrome-ms-benzdianthrone, from Application filed June 16, 1927, Serial No. 199,421, and in Germany March 15, 1826.

which the dibroine-ms-benzdianthrone corresponding most probably to the formula can be easily obtained, for instance by precipitation from a solution in concentrated sulfuric acid. The new coloring matter dissolves with a blue color in concentrated sulfuric acid and crystallizes from benzene in orange-yellow needles. Cotton is dyed from the green vat strong yellow shades.

E mample 2.

100 parts of ms-benzdianthrone and 5 parts of iodine are dissolved in 750 parts of nitrobenzene. 200 parts of bromine are added to the solution, drop by drop, while stirring at about 100 C. As soon as all or the bromine has been added, the temperature is slowly raised to about 150-160 C. and the mixture maintained at this temperature for four hours. After cooling down, the precipitate is filtered oil by suction. A, brownish-yellow powder is thus obtained, which when recrystallized from nitrobenzene gives brownish-yellow needles of tribromc-msbenzdianthrone. This substance dissolves in concentrated sulfuric acid with a bluish green color, and gives very strong goldenyellow shades on cotton.

Example 3.

150 parts of sulfuryl chlorid are added at 60 C. while stirring to a solution of 100 parts of ms-benzdianthrone in 400 to 500 parts of nitrobenzene to which about parts of iodine have been added. he mixture is stirred for 6 hours at this temperature, al lowed to cool. and filtered with suction. The remainder of the reaction product can be isolated from the filtered liquid by driving off the nitrobenzene by means of steam. The yield is quantitative; by recrystallization l'roin nitrobenzene yellow needles of trichlorins-henzdianthrone, Which dissolve in concentrated sulfuric acid with a blue color, are obtained; the product dyes cotton from the green vat strong golden-yellow shades.

Emamiplc 1 150 parts of sulfuryl chlorid are added, drop by drop, at (30 C. while stirring, to a solution of 100 parts o't 2.2-dimethyl-msl)QllZtlltlllblll'finfl in 4:00 to 500 parts of nitrobenzene to which about 5 parts of iodine have been added. After the stirring has been continued at this temperature :lor 6 hours, the reaction mixture is allowed to cool and worked up in the same way as described in Example 3. The tetrachlor-diinethyl-msbenzdianthrone corresponding most probably to the formula can he recrystallized from nitrobenZen-e to form orange colored needles. It is soluble in concentrated sulfuric acid with a bluegreen color and dyes cotton from the green vat bright orange shades.

Example 5.

10 parts of 2.:2-dimethyl-ms-benzdianthrone are dissolved in 250 parts of sulfuric acid ol? 66 lie. strength and 0.5 part of iodine added. Dry chlorine gar so long passed in at 1.00" C. until the solut .1011 which was blue at the begunnng, has turned greenish-blue in color. It is then poured onto ice and filtered with suction. 'lhe chlor-dr- Inethyl-ms-benzdranthrone thus produced terms green vats, and. dyes cotton clear orange shades.

Example 6.

parts of sulfuryl chlorid are added, drop by drop, at C. While stirring to a solution of 10 parts of elsetajl1chlor-2.i2-d1- met-liyl-nis-benzzilianthrone and 0.5 part of iodine in 100 parts of nitrobenzene. inc r action mixture is maintained at this temperature tor Six hours. It is then cooled down and the pentacl1lor-2.2-dimethyl-ms lienzdianthrene, correspondi.ng most probably to the tterniula MAX. ALBERT KUuZ. KARL KOBERLE. 

